Tantalum based single, double, and triple atom catalysts supported on g-CN monolayer for effective nitrogen reduction reaction: a comparative DFT investigation
Design of efficient and low cost electrocatalysts for the reduction of N 2 molecule to NH 3 in a green manner remains a great challenge in the 21st century. Herein, we have used density functional theory based first principle simulations to systematically investigate the nitrogen reduction reaction...
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| Published in | Catalysis science & technology Vol. 12; no. 1; pp. 31 - 319 |
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| Main Authors | , , , , , , |
| Format | Journal Article |
| Published |
04.01.2022
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| Online Access | Get full text |
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| Summary: | Design of efficient and low cost electrocatalysts for the reduction of N
2
molecule to NH
3
in a green manner remains a great challenge in the 21st century. Herein, we have used density functional theory based first principle simulations to systematically investigate the nitrogen reduction reaction (NRR) ability of single, double, and triple Ta-atom catalysts anchored to C
2
N monolayer. Our results demonstrate that the single and triple Ta-atom catalysts anchored to C
2
N monolayer act as superior catalysts for the NRR
via
alternating and distal pathways as compared to the Ru(0001) stepped surface. In particular, the triple Ta-atom catalyst anchored to C
2
N shows enhanced NRR performance with a limiting potential of −0.72 V which is comparable to the experimentally reported Ru based single atom catalyst. Further, all the three catalysts were found to be highly selective for NRR with an enhanced ability to suppress the competitive hydrogen evolution reaction. Electronic structure analysis revealed that the enhanced ability of Ta
3
@C
2
N catalyst to effectively capture and reduce N
2
molecule could be attributed to the built up of localized d states near the fermi level, thereby aiding in strong electron transfer into the antibonding orbitals of N
2
. Thus, our findings propose a highly active catalyst for the NRR with an emphasis on the importance of triple atom-based catalysts for electrocatalytic applications.
Density functional theory simulations demonstrate that single and triple Ta-atom catalysts anchored to C
2
N monolayer act as superior catalysts for the nitrogen reduction reaction
via
alternating and distal pathways. |
|---|---|
| Bibliography: | 10.1039/d1cy01292d 2 3 C and Ta p-states near the Fermi level, detailed free energy diagrams for the NRR pathways on the studied catalysts, solvation effect corrected most favourable free energy pathways, activation barriers for side-on to end-on transition for N catalysts, and coordinates of various adsorbed species along the most favourable pathways of NRR on Ta Electronic supplementary information (ESI) available: Zero-point and entropic corrections to the free energy of the gas phase and the adsorbed species along the most favourable reaction pathways, diffusion energy barrier plot of Ta atom from the cavity of g-C N to the hexagonal ring, IPDOS of Ta d-states and N adsorption on Ta n N catalysts. See DOI |
| ISSN: | 2044-4753 2044-4761 |
| DOI: | 10.1039/d1cy01292d |